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Definitions

• the present invention pertains to a reversibly thermochromic system comprising a substituted or an unsubstituted 6,11-dihydroxy-naphthacene-5,12-dione and a base and to a reversibly thermochromic composition comprising the reversibly thermochromic system and a carrier material and to novel substituted 6,11-dihydroxy-naphthacene-5,12-diones.
• EP 0438376 A1 relates to 6,11-diaryloxy-naphthacene-5,12-diones in photochromic systems. Several substituted 6,11-dihydroxy-naphthacene-5,12-diones are used as starting material for the preparation of 6,11-diaryloxy-naphthacene-5,12-diones.
• thermochromic systems consist of a basic color former such as a leuco dye and an acidic developer such as a phenolic compound. In cold, these components are a dark colored salt and upon heating they dissociate above a certain temperature. On cooling the dark colored salt forms again.
• the major drawbacks are the poor photostability of the basic color former and the acidic developer and the color change may be retarded and such systems have a reduced thermal stability which is a disadvantage in plastic articles prepared by extrusion.
• the system according to this invention does not have these disadvantages as the used compounds may have a greater photostability and less or no retarding of the color change. For instance, the color change is fully reversible and there's essentially no fatigue after many hot-cold cycles.
• the system or compound according to this invention changes color upon heating and turn back to the original color upon cooling. So at cold temperature the system or compound is in one chemical form and upon heating the system or compound changes color and is in another chemical form.
• one form is a 6,11-dihydroxy-naphthacene-5,12-dione (e.g. a compound of formula (I) as defined below) and a base and the other form is a compound of formula (II).
• the color is for example purple or blue which turns upon heating for example to orange or red.
• 6,11-Dihydroxy-naphthacene-5,12-diones are thermally quite stable so they can be extruded at high temperatures which is required for incorporation into common thermoplastic polymers.
• the present invention pertains to a reversibly thermochromic system comprising
• component a is a compound of formula (I) or one of the tautomers thereof
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently are H, C 1 -C 30 alkyl, C 7 -C 12 aralkyl, C 1 -C 30 alkoxy, C 1 -C 30 alkylthio, C 1 -C 30 alkylsulfoxyl, C 1 -C 30 alkylsulfonyl, C 2 -C 30 alkenyl, C 8 -C 12 aralkenyl, C 2 -C 30 alkenyloxy, C 2 -C 30 alkenylthio, C 2 -C 30 alkenylsulfoxyl, C 2 -C 30 alkenylsulfonyl, C 2 -C 30 alkynyl, C 8 -C 12 aralkynyl, C 2 -C 30 alkynyloxy, C 2 -C 30 alkynylthio, C 2 -C 30 alkynyl
• R 10 and R 13 are independently C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 6 -C 10 aryl, C 7 -C 12 aralkyl, C 8 -C 12 aralkenyl, C 8 -C 12 aralkynyl or an organic polymer, whereby the alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl and aralkynyl are substituted or unsubstituted;
• R 9 is H or as defined for R 10 ;
• R 11 , and R 12 are independently H or C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C
• R 15 is H or CH 3 ; q, r and s are independently integers from 1 to 20; R 16 is NH 2 , NHR 14 , or
• R 17 and R 18 are independently as defined for R 14 or
• Compounds of formula (I) may form tautomers of formula (101), (102) and/or (103).
• the units that are x, y and z times part of the molecule may be distributed randomly in the oligomer or in the polymer, with the proviso that no group L is directly connected to another group L and that no group L′ is directly connected to another group L′.
• R 1 , R 4 , R 5 and R 8 not being COO—CH 3 and COO—CH 2 CH 3 , for example not being COO—R 9 with R 9 ⁇ C 1 -C 4 alkyl, especially with R 9 being alkyl, in particular not being COOR 9 .
• the alkyl mentioned in this paragraph is for example unsubstituted, in particular unsubstituted or substituted.
• substituents R 2 , R 3 , R 6 and R 7 not being COO-isobutyl and COO—CH 2 CH 2 —O—C 2 CH 3 , for example not being COO—R 9 with R 9 being substituted ethyl or unsubstituted butyl (e.g. branched, for instance branched or linear), in particular not being COO—R 9 with R 9 being unsubstituted or substituted C 2 -C 4 alkyl (e.g. unsubstituted or substituted C 1 -C 5 alkyl, in particular substituted or unsubstituted alkyl), especially not being COO—R 9 .
• R 9 being substituted ethyl or unsubstituted butyl (e.g. branched, for instance branched or linear), in particular not being COO—R 9 with R 9 being unsubstituted or substituted C 2 -C 4 alkyl (e.g. unsubstituted or substitute
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is to be understood that the two adjacent groups are connected to two carbon atoms which are directly connected to each other.
• substituents R 1 -R 8 only one or two substituents R 1 -R 8 contain groups R 9 , R 10 or R 13 being an organic polymer, especially only one of the substituents R 1 -R 8 contains said groups.
• R 1 and R 4 or R 2 and R 3 contain groups R 9 , R 10 or R 13 being an organic polymer, e.g. only R 2 and R 3 contain said groups.
• R 1 or R 2 contain a group R 9 , R 10 or R 13 being an organic polymer, in particular only R 2 contains said group.
• organic polymers as R 9 , R 10 or R 13 that are synthetic organic polymers.
• organic polymers as R 9 , R 10 or R 13 that contain at least one functional group such as OH, NH 2 , NH, CONH 2 , COO-alkyl (e.g. C 1 -C 30 alkyl, in particular methyl) and/or COOH prior to reaction and upon reaction form an ester or an amide group with the help of another appropriate functional group.
• organic polymers as R 9 , R 10 or R 13 that contain acrylic units or vinyl groups, for example acrylic polymer or copolymer or polyolefins.
• Examples of organic polymers as R 9 , R 10 or R 13 are the polymers mentioned in the list below as items 1.-3., 5.-6a., 7., 9.-14., 18., 24. and 25.
• alkyl comprises within the limits of the carbon atoms given, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, 2-methylheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl and dodecyl.
• alkyl comprises cycloalkyl such as cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, dimethylcyclopentyl and methylcyclohexyl.
• alkyl does not comprise cycloalkyl.
• alkenyl examples include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl and dodecenyl.
• alkenyl also comprises residues with more than one double bond that may be conjugated or non-conjugated.
• alkynyl examples are ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl and dodecynyl.
• alkynyl comprises residues with one or more triple bonds with optionally one or more double bonds whereby the unsaturated bonds may be conjugated or non-conjugated.
• alkylene examples include methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, 2-ethylbutylene, n-pentylene, isopentylene, 1-methylpentylene, 1,3-dimethylbutylene, n-hexylene, 1-methylhexylene, n-heptylene, 2-methylheptylene, 1,1,3,3-tetramethylbutylene, 1-methylheptylene, 3-methylheptylene, n-octylene, 2-ethylhexylene, 1,1,3-trimethylhexylene, 1,1,3,3-tetramethylpentylene, nonylene, decylene, undecylene, 1-methylundecylene and dodecylene.
• alkenylene examples are within the limits of the carbon atoms given vinylene, allylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene and dodecenylene.
• alkenylene also comprises residues with more than one double bond that may be conjugated or non-conjugated.
• Aryl is for instance phenyl whereas aralkyl is for example benzyl.
• An example of an aralkenyl is 2-phenylethenyl
• an example of an aralkynyl is 2-phenylethynyl.
• arylene is phenylene.
• alkoxy, alkylthio, alkylsulfoxyl or alkylsulfonyl means that an alkyl group as defined above with appropriate number of carbon atoms is connected to O, S, SO or S( ⁇ O) 2 respectively.
• alkenyloxy, alkenylthio, alkenylsulfoxyl or alkenylsulfonyl means that an alkenyl group as defined above with appropriate number of carbon atoms is connected to O, S, SO or S( ⁇ O) 2 respectively.
• alkynyloxy, alkynylthio, alkynylsulfoxyl or alkynylsulfonyl means that an alkynyl group as defined above with appropriate number of carbon atoms is connected to O, S, SO or S( ⁇ O) 2 respectively.
• C 6 -C 10 aryloxy, C 6 -C 10 arylthio, C 6 -C 10 arylsulfoxyl or C 6 -C 10 arylsulfonyl means that an aryl group as defined above with appropriate number of carbon atoms is connected to O, S, SO or S( ⁇ O) 2 respectively.
• halogen examples include F, Cl, Br and I, especially Cl and Br, in particular Cl.
• thermochromic system Of particular interest is a reversibly thermochromic system, wherein
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently are H, C 1 -C 30 alkyl, C 7 -C 12 aralkyl, C 1 -C 30 alkoxy, C 1 -C 30 alkylthio, C 1 -C 30 alkylsulfoxyl, C 1 -C 30 alkylsulfonyl, C 2 -C 30 alkenyl, C 8 -C 12 aralkenyl, C 2 -C 30 alkenyloxy, C 2 -C 30 alkenylthio, C 2 -C 30 alkenylsulfoxyl, C 2 -C 30 alkenylsulfonyl, C 2 -C 30 alkynyl, C 8 -C 12 aralkynyl, C 2 -C 30 alkynyloxy, C 2 -C 30 alkynylthio, C 2 -C 30 alkynyl
• the part of the one substituent with the open bracket and the part of the other substituent with the open bracket form together with the part of the molecule they are both attached to a monomer unit that is x times part in an oligomer or polymer; q, r and s are independently integers from 1 to 5; with the other substituents being as defined above.
• thermochromic system Of special interest is a reversibly thermochromic system, wherein
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently are H, C 1 -C 30 alkyl, C 7 -C 12 aralkyl, C 1 -C 30 alkoxy, C 1 -C 30 alkylthio, C 1 -C 30 alkylsulfoxyl, C 1 -C 30 alkylsulfonyl, C 2 -C 30 alkenyl, C 8 -C 12 aralkenyl, C 2 -C 30 alkenyloxy, C 2 -C 30 alkenylthio, C 2 -C 30 alkenylsulfoxyl, C 2 -C 30 alkenylsulfonyl, C 2 -C 30 alkynyl, C 8 -C 12 aralkynyl, C 2 -C 30 alkynyloxy, C 2 -C 30 alkynylthio, C 2 -C 30 alkynyl
• R 24 is C 2 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 6 -C 10 aryl, C 7 -C 12 aralkyl, C 8 -C 12 aralkenyl, C 8 -C 12 aralkynyl or
• alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl and aralkynyl are substituted or unsubstituted as defined above;
• q is an integer from 2 to 4;
• r and s are independently integers from 1 to 3;
• W is C 6 -C 10 arylene, C 1 -C 30 alkylene, C 1 -C 30 alk-1-enylene, NR 11 or O;
• R 25 is H or C 1 -C 4 alkyl; with the other substituents being as above.
• thermochromic system wherein
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently are H, C 1 -C 30 alkyl, C 7 -C 12 aralkyl, C 1 -C 30 alkoxy, C 1 -C 30 alkylthio, C 1 -C 30 alkylsulfoxyl, C 1 -C 30 alkylsulfonyl, C 6 aryl, C 6 arylthio, C 6 arylsulfoxyl, C 6 arylsulfonyl, halogen, COO—R 9 , OCO—R 10 , whereby the alkyl and aryl are substituted or unsubstituted, or R 2 and R 3 form a 5- or 6-membered alicyclic or heterocyclic ring structure together with the two carbon atoms they are directly connected to that is R 2 and R 3 form together the group CO—O—CO or CO—NR 24 —CO; or R 2 and R 3
• R 10 is C 1 -C 30 alkyl or C 6 aryl, whereby the alkyl and aryl is substituted or unsubstituted;
• R 9 is H or as defined for R 10 ;
• R 24 is unsubstituted or substituted C 2 -C 30 alkyl or C 6 aryl;
• V is SO 2 ;
• G 1 is C 2 -C 10 alkylene;
• L and L′ are A or B; if L is A, then L′ is B; if L is B, then L′ is A;
• A is O;
• B CO;
• G 2 is C 2 -C 10 alkylene;
• G 3 has the same meanings as G 2 ;
• x and y are independently integers from
• thermochromic system wherein
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently are H, C 1 -C 30 alkylthio, C 1 -C 30 alkylsulfonyl, COO—R 9 , C 6 aryl, whereby the alkyl is substituted or unsubstituted,
• R 2 and R 3 form a 5- or 6-membered alicyclic or heterocyclic ring structure together with the two carbon atoms they are directly connected to that is R 2 and R 3 form together the group CO—O—CO or CO—NR 24 —CO;
• R 2 and R 3 are defined as follows:
• thermochromic system Of most particular interest is a reversibly thermochromic system, wherein
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently are H, C 2 -C 20 alkylthio, C 2 -C 20 alkylsulfonyl, COO—R 9 , C 6 aryl, whereby the alkyl is substituted or unsubstituted,
• R 2 and R 3 form a 5- or 6-membered alicyclic or heterocyclic ring structure together with the two carbon atoms they are directly connected to that is R 2 and R 3 form together the group CO—O—CO or CO—NR 24 —CO;
• R 9 is H or C 3 -C 20 alkyl, whereby the alkyl is substituted or unsubstituted;
• R 24 is unsubstituted or substituted C 4 -C 20 alkyl or C 6 aryl
• substituted alkyl and substituted aryl are substituted by hydroxy and/or COO—R 21 ; or the aryl is substituted by C 1 -C 15 alkyl;
• R 21 is H or C 1 -C 15 alkyl.
• An example is a reversibly thermochromic system, wherein one to four substituents R 1 -R 8 are not H.
• Another example is a reversibly thermochromic system, wherein R 1 , R 4 , R 5 and R 8 are H and R 2 , R 3 , R 6 and R 7 are not H.
• a further example is a reversibly thermochromic system, wherein R 1 and R 4 -R 8 are H and R 2 and R 3 are not H.
• Another example is a reversibly thermochromic system, wherein R 1 and R 3 -R 8 are H and R 2 is not H.
• thermochromic system Of utmost interest is a reversibly thermochromic system, wherein
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is or contains a sulfoxyl, a sulphonyl, an ester, an ether or an amide group, whereby if the sulphonyl group is phenylsulphonyl, at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are phenylsulphonyl, or two groups of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are carboxy, or two adjacent groups of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 form a 5- or 6-membered cyclic ring structure that is not maleic acid methyl imide or benzene or the compound of formula (I) is an oligomer or a polymer.
• Maleic acid methyl imide and benzene means that said residues are formed by two adjacent groups of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 together with the two carbon atoms the two adjacent groups are directly connected to.
• the compound of formula (I) is an oligomer or a polymer means that it is part of an oligomer or polymer.
• thermochromic system wherein the base b has a molecular weight of at least 300.
• the molecular weight is expressed in grams per mole.
• a reversibly thermochromic system wherein the base b is an secondary or tertiary amine or a secondary or tertiary phosphine, whereby said amine and said phosphine are not aromatic and do not have aromatic substituents that are directly connected to said amine or said phosphine.
• the secondary or tertiary amine or the secondary or tertiary phosphine has two or three organic substituents.
• the secondary amine is NHR 26 R 27
• the tertiary amine is NR 26 R 27 R 28
• the secondary phosphine is PHR 26 R 27
• the tertiary phosphine is PR 26 R 27 R 28
• R 26 , R 27 and R 28 are independently an organic residue containing 1-500 carbon atoms and optionally 1-200 heteroatoms, in particular N, P, O, S, Se, Cl, Br and/or I; or R 26 and R 27 form together with the N they are connected to an optionally substituted 5- or 6-membered cyclic ring structure; for instance, such an optionally substituted cyclic ring structure is a sterically hindered amine;
• the secondary or tertiary amine or the secondary or tertiary phosphine does not contain acidic groups such as COOH and SO 2 OH.
• R 26 , R 27 and R 28 are independently C 1 -C 30 alkyl, C 7 -C 12 aralkyl, C 2 -C 30 alkenyl, C 8 -C 12 aralkenyl, C 2 -C 30 alkynyl or C 8 -C 12 aralkynyl, the said groups are unsubstituted or substituted by one or more COO—R 21 , CONR 21 R 22 , OCO—R 23 , NR 21 CO—R 23 , NR 23 R 21 , O—R 23 , S—R 23 , SO—R 23 and/or S( ⁇ O) 2 —R 23 ; or the aralkyl, aralkenyl and aralkynyl are substituted by C 1 -C 30 alkyl, C 2 -C 30 alkenyl and/or C 2 -C 30 alkynyl; or the said amine is a sterically hindered amine; R 21 , R 22
• the base b is a secondary or tertiary amine, for instance a secondary amine, for example a secondary or tertiary sterically hindered amine such as a secondary sterically hindered amine.
• the secondary or tertiary sterically hindered amine is preferably a compound of formula (III)
• G 4 , G 5 , G 6 and G 7 are independently methyl or ethyl, for example methyl;
• E is hydrogen, C 1 -C 18 alkyl or C 3 -C 18 alkenyl, for example C 1 -C 18 alkyl or hydrogen, in particular hydrogen;
• E 10 is a carbon atom which is unsubstituted or substituted by OH, ⁇ O or by one or two organic residues containing in total 1-500 carbon atoms.
• the secondary or tertiary sterically hindered amine is preferably one of formulae (A) to (M)
• E, G 4 , G 5 , G 6 and G 7 are as defined above; m is 0 or 1; R 29 is hydrogen, hydroxyl or hydroxymethyl; R 30 is hydrogen, alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12 carbon atoms; a is 1 to 4; when a is 1, R 31 is hydrogen, alkyl of 1 to 18 carbon atoms, alkoxycarbonylalkylenecarbonyl of 4 to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2-(hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkyl is interrupted by oxygen, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, or acy
• R 38 is hydrogen or methyl, c is 2 to 8, R 39 and R 40 are independently hydrogen or the group T 2 , T 2 is
• e is 1 to 10, for example 2-10; d is an integer such that the compound has a molecular weight of 1000 to 4000 amu, e.g. d may be from the range 3-10;
• R 41 is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to 10 carbon atoms, especially branched alkylamino of 3 to 8 carbon atoms such as tert-octylamino, —N(alkyl)T 1 with alkyl of 1 to 8 carbon atoms, or —N(alkyl) 2 of 2 to 16 carbon atoms,
• R 42 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted once by chlorine and once by R 41 , or s-triazinyl substituted twice by R 41 with the condition that the two R 41 substituents may be different;
• R 43 is chlorine
• R 45 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted twice by —N(alkyl) 2 of 2 to 16 carbon atoms or s-triazinyl substituted twice by —N(alkyl)T 1 with alkyl of 1 to 8 carbon atoms;
• R 44 is independently hydrogen, alkyl of 1 to 18 carbon atoms, alkoxycarbonylalkylene-carbonyl of 4 to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxy-propyl, 2-hydroxy or 2-(hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkyl is interrupted by oxygen, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloali
• the secondary or tertiary sterically hindered amine is more preferably of formula (D) or (L), in particular of formula (L).
• the secondary or tertiary sterically hindered amine is of formula (C).
• a is 1 or 2, preferably 2;
• R 31 is hydrogen, alkyl of 1 to 18 carbon atoms or an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, preferably R 31 is alkyl of 1 to 18 carbon atoms or an acyl radical of an aliphatic carboxylic acid containing 2 to 18 carbon atoms, most preferably R 31 is an acyl radical of an aliphatic carboxylic acid containing 2 to 18 carbon atoms; when a is 2, R 31 is alkylene of 2 to 18 carbon atoms or a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, preferably R 31 is alkylene of 2 to 18 carbon atoms or a divalent acyl radical of an aliphatic dicarboxylic acid containing 2 to 18 carbon atoms, most preferably R 31 is a divalent acyl radical of an
• p is 1 or 2, preferably 2;
• R 32 is hydrogen or alkyl of 1 to 18 carbon atoms, preferably hydrogen
• R 33 is alkyl of 1 to 18 carbon atoms or an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, for example R 33 is alkyl or an acyl radical of an aliphatic carboxylic acid containing 2 to 18 carbon atoms; when p is 2, R 33 is alkylene of 2 to 12 carbon atoms or a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, for instance R 33 is alkylene of 2 to 12 carbon atoms.
• c 4 to 8;
• R 41 is alkylamino of 1 to 10 carbon atoms, especially branched alkylamino of 3 to 8 carbon atoms such as tert-octylamino, —N(alkyl)T 1 with alkyl of 1 to 8 carbon atoms, or —N(alkyl) 2 of 2 to 16 carbon atoms;
• R 42 is hydrogen, s-triazinyl substituted once by chlorine and once by R 41 or s-triazinyl substituted twice by R 41 with the condition that the two R 41 substituents may be different, for example R 42 is hydrogen or s-triazinyl substituted twice by R 41 ;
• R 43 is as described above, for example R 43 is the group T 3 ,
• R 45 of the group T 3 is hydrogen, s-triazinyl substituted twice by —N(alkyl) 2 of 2 to 16 carbon atoms or s-triazinyl substituted twice by —N(alkyl)T 1 with alkyl of 1 to 8 carbon atoms, for example R 45 of the group T 3 is hydrogen or s-triazinyl substituted twice by —N(alkyl) 2 of 2 to 16 carbon atoms.
• TINUVIN® 622 (CAS 65447-77-0), HOSTAVIN® N 30 (CAS 202483-55-4), FERRO® AM 806 (CAS 70800-09-8), DASTIB® 845 (CAS 24860-22-8), TINUVIN® 770 (CAS 58829-07-9), TINUVIN® 765 (CAS 82919-37-7 and 41556-26-7), TINUVIN® 144 (CAS 63843-89-0), ADK STAB® LA 52 (CAS 91788-83-9), ADK STAB® LA 57 (CAS 64022-61-3), ADK STAB® LA 62 (CAS 107119-91-5), ADK STAB® LA 67 (CAS 100631-43-4), HOSTAVIN® N 20 (CAS 64338-16-5), HOSTAVIN® N 24 (CAS 85099-51-0 and 85099-50-9), SANDUVOR® 3050 (CAS 85099-51-0 and 85099
• Chimassorb® 944 (CAS 71878-19-8) or Chimassorb® 2020 (CAS 192268-64-7) or Tinuvin® 770 (CAS 58829-07-9), especially Chimassorb® 944 or Chimassorb® 2020.
• an aliphatic carboxylic acid is acetic, propionic, butyric, stearic acid.
• An example of a cycloaliphatic carboxylic acid is cyclohexanoic acid.
• An example of an aromatic carboxylic acid is benzoic acid.
• An example of an aliphatic dicarboxylic acid is malonyl, maleoyl, succinyl, adipic or sebacic acid.
• An example of a residue of an aromatic dicarboxylic acid is phthaloyl.
• Acyl radicals of monocarboxylic acids are, within the definitions, a residue of the formula —CO—R′′, wherein R′′ may stand inter alia for an alkyl, alkenyl, cycloalkyl or aryl radical as defined.
• Preferred acyl radicals include acetyl, benzoyl, acryloyl, methacryloyl, propionyl, butyryl, valeroyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, pentadecanoyl, stearoyl.
• Polyacyl radicals of polyvalent acids are of the formula (—CO) n1 —R′′, wherein n1 is the valency, e.g. 2, 3, 4, 5 or 6.
• the ratio of component a to component b is preferably 2:1 to 1:100 by weight, more preferably 1:1 to 1:20 by weight, most preferably 1:2 to 1:16 by weight, for example 1:3 to 1:6 by weight.
• This invention also relates to a compound of formula (II) or one of its tautomers
• R 1 -R 8 are as defined above;
• M + is an ammonium cation or a phosphonium cation with the proviso that the ammonium cation and the phosphonium cation are not aromatic and do not have aromatic substituents which are directly connected to said ammonium cation or said phosphonium cation.
• the compound of formula (II) may form tautomers.
• these tautomers are compounds of formulae (104)-(110)
• M + is a secondary or tertiary ammonium cation or a secondary or tertiary phosphonium cation.
• M + has a molecular weight of at least 150, more preferably of at least 300, most preferably of at least 350.
• M + being a secondary or tertiary ammonium cation, for example a secondary ammonium cation, in particular a secondary or tertiary sterically hindered ammonium cation, e.g. a secondary sterically hindered ammonium cation.
• these secondary or tertiary ammonium cation or a secondary or tertiary phosphonium cation or a secondary or tertiary sterically hindered ammonium cation correspond to the secondary or tertiary amine or the secondary or tertiary phosphine or the secondary or tertiary sterically hindered amine as defined above that carry an additional H + at the amine or phosphine functional group.
• Another embodiment of this invention is a reversibly thermochromic composition, comprising
• thermochromic system as above or a compound of formula (II) as above
• the ratio of component i to component ii is preferably 1:10000 to 1:1, more preferably 1:5000 to 1:2, most preferably 1:1000 to 1:5.
• the carrier material ii is polymers, solvents and/or waxes.
• the carrier material ii is plastic articles, films, papers, fibers, solvents, waxes, coatings and/or inks.
• Example of polymers suitable as carrier material ii are
• Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
• HDPE high density polyethylene
• HDPE-HMW high density and high molecular weight polyethylene
• HDPE-UHMW high density and ultrahigh molecular weight polyethylene
• MDPE medium density polyethylene
• LDPE low density
• Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
• Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g.
• ethylene/norbornene like COC ethylene/1-olefins copolymers, where the 1-olefin is gene-rated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate cop
• Hydrocarbon resins for example C 5 -C 9
• hydrogenated modifications thereof e.g. tackifiers
• mixtures of polyalkylenes and starch
• Homopolymers and copolymers from 1.)-4.) may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
• Polystyrene poly(p-methylstyrene), poly( ⁇ -methylstyrene).
• Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
• Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of sty
• Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6. especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
• PCHE polycyclohexylethylene
• PVCH polyvinylcyclohexane
• Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
• Graft copolymers of vinyl aromatic monomers such as styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; st
• Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
• Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
• Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
• Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
• Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
• Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol
• Polyureas Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
• Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
• Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
• Crosslinkable acrylic resins derived from substituted acrylates for example epoxy acrylates, urethane acrylates or polyester acrylates.
• Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
• Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
• Blends of the aforementioned polymers for example PP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
• polyblends for example PP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/
• incorporation into the organic polymers can be effected, for example, by mixing in or applying to a 6,11-dihydroxy-naphthacene-5,12-dione and a base or by mixing in or applying to a compound of formula (II) and, if desired, further additives by the methods which are customary in the art.
• the incorporation can take place prior to or during the shaping operation, or by applying the dissolved or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as lattices.
• a further possibility for incorporating the compounds mentioned above into polymers is to add them before, during or directly after the polymerization of the corresponding monomers or prior to crosslinking.
• the compounds mentioned above can be added as it is or else in encapsulated form (for example in waxes, oils or polymers).
• the compounds mentioned herein can also be added in the form of a masterbatch containing said compound in a concentration, for example, of from 2.5 to 25% by weight to the carrier material ii.
• a 6,11-dihydroxy-naphthacene-5,12-dione and a base, or a compound of formula (II), with or without further additives, can also be sprayed onto the carrier material ii such as plastic article, fiber, film, paper or coating. It is able to dilute other additives (for example the conventional additives indicated above) or their melts so that they too can be sprayed together with these additives onto the carrier material ii.
• thermochromic composition as defined above, comprising further additives.
• the further additives are:
• antioxidants UV-absorbers, light stabilizers, metal deactivators, processing stabilizers, thiosynergists, peroxide scavengers, oxygen scavengers, basic co-stabilizers, nucleating agents, fillers, reinforcing agents, flameproofing agents and/or additional colorants with the proviso that the additional colorants do not suppress and do not mask the thermochromic effect.
• phenolic antioxidants aminic antioxidants, phosphites, phosphonites, hydroxylamines, nitrones, benzofuranones, indolinones, 2-(2-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, 2-(2-hydroxyphenyl)-1,3,5-triazines, oxamides, sterically hindered amines, pigments and/or dyes.
• Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl-phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol
• Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethyl phenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
• Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.
• 2,6-di-tert-butyl-4-methoxy-phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl
• Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
• Hydroxylated thiodiphenyl ethers for example 2, 2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octyl phenol), 4,4′-thiobis(6-tert-butyl-3-methyl phenol), 4,4′-thiobis(6-tert-butyl-2-methyl phenol), 4,4′-thiobis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.
• Hydroxylated thiodiphenyl ethers for example 2, 2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octyl phenol), 4,4′-thiobis(6-tert-butyl-3-methyl phenol), 4,4′-thiobis(6-tert-butyl-2-methyl phenol), 4,4′-thiobis
• Alkylidenebisphenols for example 2, 2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)-phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4,6-di-tert-butyl-phenol), 2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-( ⁇ -methyl benzyl)-4-nonylphenol], 2,2′-methylenebis[6-( ⁇ , ⁇ -dimethyl benzyl)-4-iso
• O-, N- and S-benzyl compounds for example 3, 5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
• Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
• Aromatic hydroxybenzyl compounds for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethyl benzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
• Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri-azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tri-tri
• Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
• Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
• esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol-propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo
• esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly-hydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo
• esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, tri-ethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)ox-amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
• esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)ox-amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
• Aminic antioxidants for example N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-
• 2-(2′-Hydroxyphenyl)benzotriazoles for example 2-(2′-hydroxy-5′-methylphenyl)-benzo-triazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethyl butyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyl
• R 3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl, 2-[2′-hydroxy-3′-( ⁇ , ⁇ -dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)-phenyl]-benzotriazole; 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-( ⁇ , ⁇ -dimethyl benzyl)-phenyl]benzotriazole.
• 2-Hydroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl-oxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.
• Esters of substituted and unsubstituted benzoic acids for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo-ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butyl phenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
• Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate, methyl ⁇ -carbomethoxy-p-methoxycinnamate, N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline, neopentyl tetra( ⁇ -cyano- ⁇ , ⁇ -di-phenylacrylate.
• Nickel compounds for example nickel complexes of 2,2′-thio-bis[4-(1,1,3,3-tetramethyl-butyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
• additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarba
• Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,
• Oxamides for example 4, 4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
• Metal deactivators for example N,N′-diphenyloxamide, N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyl dihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.
• Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphit
• Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos®168, Ciba Specialty Chemicals Inc.), tris(nonylphenyl)phosphite,
• Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethyl hydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecyl hydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxy-ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkyl hydroxylamine derived from hydrogenated tallow amine.
• Nitrones for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptyinitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta-decylnitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrone derived from N,N
• Thiosynergists for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.
• Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ -dodecylmercapto)propionate.
• esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
• mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole zinc dibutyldithiocarbamate
• dioctadecyl disulfide pentaerythritol tetrakis( ⁇ -dodecyl
• Polyamide stabilizers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
• Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
• Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ric
• Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
• inorganic substances such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
• organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
• polymeric compounds such as ionic copolymers (
• Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car-bon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
• additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
• the further additives are judiciously employed in amounts of 0.1-10% by weight, for example 0.2-5% by weight, based on the carrier material ii.
• Another embodiment of this invention is the use of a 6,11-dihydroxy-naphthacene-5,12-dione in combination with a base or the use of a compound of formula (II) as defined above as a reversibly thermochromic colorant in a reversibly thermochromic system.
• Another embodiment of this invention is a process for reversibly thermochromically coloring a carrier by applying thereto/incorporating therein a 6,11-dihydroxy-naphthacene-5,12-dione and a base or by applying thereto/incorporating therein a compound of formula (II) as defined above.
• a further embodiment of this invention is a compound of formula (I) or one the tautomers thereof as defined above, wherein
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is or contains a sulfoxyl, a sulphonyl, an ester, an ether or an amide group, whereby if the sulphonyl group is phenylsulphonyl, at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are phenylsulphonyl or
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are carboxy or
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 form a 5- or 6-membered cyclic ring structure that is not maleic acid methyl imide or benzene or
• the compound of formula (I) is an oligomer or a polymer with the proviso that one of R 2 , R 3 , R 6 and R 7 cannot be COOR 9 with R 9 being isobutyl or 2-ethoxyethyl if the other seven substituents R 1 -R 8 are hydrogen.
• Another embodiment of this invention is a compound of formula (I) or one the tautomers thereof as defined above, wherein
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is or contains a sulfoxyl, a sulphonyl, an ester, an ether or an amide group, whereby if the sulphonyl group is phenylsulphonyl, at least
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are phenylsulphonyl or
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are carboxy or
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 form a 5- or 6-membered cyclic ring structure that is not maleic acid methyl imide or benzene or the compound of formula (I) is an oligomer or a polymer.
• R 2 , R 3 , R 6 and R 7 cannot be COOR 9 with R 9 being butyl (e.g. branched, in particular branched or linear), especially R 9 being unsubstituted or substituted C 2 -C 4 alkyl, in particular R 9 being unsubstituted or substituted C 1 -C 30 alkyl (e.g. cannot be COOR 9 , in particular an ester group), if the other seven substituents R 1 -R 8 are hydrogen.
• R 9 being butyl (e.g. branched, in particular branched or linear), especially R 9 being unsubstituted or substituted C 2 -C 4 alkyl, in particular R 9 being unsubstituted or substituted C 1 -C 30 alkyl (e.g. cannot be COOR 9 , in particular an ester group), if the other seven substituents R 1 -R 8 are hydrogen.
• R 2 , R 3 , R 6 and R 7 cannot be COOR 9 with R 9 being isobutyl (e.g. branched butyl, in particular branched or linear butyl) or 2-ethoxyethyl, in particular being unsubstituted or substituted C 2 -C 4 alkyl, especially being unsubstituted or substituted alkyl.
• R 9 being isobutyl (e.g. branched butyl, in particular branched or linear butyl) or 2-ethoxyethyl, in particular being unsubstituted or substituted C 2 -C 4 alkyl, especially being unsubstituted or substituted alkyl.
• substituents R 2 , R 3 , R 6 and R 7 are substituents R 2 , R 3 , R 6 and R 7 not being COO—R 9 , in particular not being an ester group.
• R 2 , R 3 , R 6 and R 7 outlined above are eligible for R 1 -R 8 .
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is or contains a sulfoxyl, a sulphonyl, an ether or an amide group, whereby if the sulphonyl group is phenylsulphonyl, at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are phenylsulphonyl or two adjacent groups of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 form a 5- or 6-membered cyclic ring structure that is not maleic acid methyl imide or benzene or the compound of formula (I) is an oligomer or a polymer.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a sulfoxyl, a sulphonyl, an ester, an ether or an amide group, whereby if the sulphonyl group is phenylsulphonyl, at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are phenylsulphonyl or
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are carboxy or
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 form a 5- or 6-membered cyclic ring structure that is not maleic acid methyl imide or benzene or
• the compound of formula (I) is an oligomer or a polymer.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is or contains a sulfoxyl group.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is or contains a sulphonyl group, whereby if the sulphonyl group is phenylsulphonyl, at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are phenylsulphonyl.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is or contains a phenyl sulphonyl.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is or contains an ester group.
• at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are or contain an ester group.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is or contains an ether group.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is or contains an amide group.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are carboxy.
• two groups of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are carboxy.
• more than two groups of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are carboxy.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 form a 5- or 6-membered cyclic ring structure that is not maleic acid methyl imide or benzene.
• the cyclic ring structure is a maleic acid anhydride.
• the cyclic ring structure is a maleic acid imide.
• the cyclic structure is not a maleic acid imide.
• the cyclic structure is not an aryl.
• the compound of formula (I) is an oligomer or a polymer.
• the compounds described herein can be synthesized according to methods known in the art from known starting materials, see for example EP 0438376 A1. Some of the compounds described herein are commercially available.
• Compounds of formula (II) can be prepared by mixing a) a compound of formula (I) or one of the tautomers thereof with b) a phosphinic or aminic base and reacting them together:
• thermochromic system or composition or compound of formula (II) as mentioned above may be used to indicate temperature changes in appliances or devices.
• the temperature change effects color changes which may be assessed by the human eye or by optical devices resulting in an effect signal.
• thermochromic systems or compositions or compounds of formula (II) as described above is in the market of household appliances. For safety reasons there is often the need that the heated part of a certain device is evidenced through the appearance of a different and clearly distinguishable color.
• thermochromic systems or compositions or compounds of formula (II) can be used in large appliances like cook-tops, dryers, ovens, space heaters, steam cleaners, dishwashers and washing machines.
• thermochromic system or composition or compound of formula (II)
• composition or compound of formula (II) is not limited to the incorporation into plastic parts of household appliances, but may find application also in many other contexts, for example:
• Percentages given are weight percentages unless otherwise stated. Percentages are given in percentages of the formulation, composition and/or combination unless otherwise stated.
• the starting material 2,3-bis(dodecylthio)-6,11-dihydroxy-naphthacene-5,12-dione, is prepared as follows:
• This product is prepared from 2,3,8,9-tetrakis(n-dodecylthio)-6,11-dihydroxy-naphthacene-5,12-dione, similarly to Example 2, yielding 36% of a dark red product, m.p. 180-183°.
• the starting material 2,3-bis(4′-hydroxybutylthio)-6,11-dihydroxy-naphthacene-5,12-dione, is prepared as follows:
• 2,3-Bis(6′-acetoxyhexylsulfonyl)-6,11-dihydroxy-naphthacene-5,12-dione 1 g (1.6 mmoles) of 2,3-bis(6′-hydroxyhexylsulfonyl)-6,11-dihydroxy-naphthacene-5,12-dione (product of Example 4e) is acetylated by a mixture of 5 ml acetic acid, 0.36 g (3.55 mmoles) of acetic anhydride, and 2 drops of sulfuric acid, at 960 for 3.5 h. The mixture is diluted with water and filtered.
• the starting material 2,3-bis(3′-carboethoxy-propyl-1-thio)-6,11-dihydroxy-naphthacene-5,12-dione, is prepared as follows:
• the starting material 4-(2′-ethyl-hexyl-1-oxycarbonyl-)-phthalic anhydride, is prepared as follows:
• Formulation 1 1.4 g of product of Example 2 corresponding to 0.2% of the total amount of the formulation and 21 g of poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[2,2,6,6-tetramethyl-4-piperidinyl)imino]] (base 1; Chimassorb® 944), corresponding to 3.0%, are mixed in a turbomixer with 677.6 g of polypropylene powder (Basell Moplen HP500H) having a melt index of 1.8 (measured at 230° and 2.16 Kg).
• Base 1 Chimassorb® 944
• the mixture is extruded at 190-230° to give polymer granules which are subsequently converted into plaques (1 mm thick), using a press-molding machine (Pasadena P210 C) operating at a maximum temperature of 240° and pressure of 20000 lb.
• a press-molding machine Pasadena P210 C
• formulation 4 containing: 0.9 g of product of Example 1 corresponding to 0.3% of the total amount of the formulation; 13.5 g of base 1 corresponding to 4.5% and 285.6 g of PP Moplen HP500H.
• the changes of the colorimetric values show how efficiently the color of the plaques changes with temperature.
• Formulation 5 containing 0.35 g of product of Example 2 corresponding to 0.05% of the total amount of the formulation, 1.75 g of 1,6-hexanediamine,N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-polymer with 2,4,6-trichloro-1,3,5-triazine, reaction products with N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine (base 2; Chimassorb® 2020), corresponding to 0.25% and 697.9 g of PP Moplen HP500H;
• formulation 6 containing 0.35 g of product of Example 2 corresponding to 0.05% of the total amount of the formulation, 0.819 g of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (base 3; Tinuvin® 770), corresponding to 0.117% and 698.831 g of PP Moplen HP500H;
• formulation 7 containing 0.35 g of product of Example 2 corresponding to 0.05% of the total amount of the formulation, 0.798 g of bis(tridecyl)amine (base 4), corresponding to 0.114% and 698.852 g of PP Moplen HP500H.
• Formulations 5-7 are extruded as described above and the granules are pressmolded in the same conditions as above to produce plaques (2 mm thick). The plaques are heated in order to induce the color change and their visual appearance is reported in the table below:
• Formulation 8 10 mg of product of Example 2d and 150 mg of base 1 (see formulation 1 above) are dissolved in 1.0 g of a mixture of ethylene-vinylacetate polymer with hydrocarbon resins (hotmelt adhesive Nr. 6630.365 marketed by Migros Inc., 8031 Switzerland) at 160°. Part of the clear red hot mixture is pressed between two glass plates resulting in a polymer spot which is blue at 25° and bright red at >100°. The heating/cooling cycle can be repeated >50 times without loss of the thermochromic characteristics.
• hydrocarbon resins hotmelt adhesive Nr. 6630.365
• Formulation 9 The formulation 8 is repeated using product of Example 4f instead of Example 2d, with the same result.
• Formulation 10 The formulation 8 is repeated using product of Example 7 instead of Example 2d, with the same result.
• Formulation 11 The formulation 8 is repeated using product of Example 7a instead of Example 2d, with the same result.
• Formulation 12 The formulation 8 is repeated using product of Example 2 instead of Example 2d, with the same result.
• Formulation 13 10 mg of product of Example 4 and 150 mg of base 1 are dissolved in 2 ml of acetone. A piece of commercial lab filter paper is dropwise treated with a part of this solution. The solvent is evaporated in a warm air stream. The residual spot on the paper is dark blue at 25° and red at >80°. The heating/cooling cycle can be repeated >50 times without loss of the thermochromic characteristics.
• thermochromic characteristics When a piece of commercial cotton fabric is treated similarly with the above-mentioned solution a similar result is obtained after drying.
• the heating/cooling cycle can be repeated >50 times without loss of the thermochromic characteristics.
• the residual stain is blue at 25° and red at >100°.
• the heating/cooling cycle can be repeated >50 times without loss of the thermochromic characteristics.
• Formulation 14 Formulation 13 is repeated using product of Example 4e instead of Example 4 and dichloromethane instead of acetone as solvent, with similar results.

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